Methods of producing stable novel black polyurethane articles with polymeric colorants

ABSTRACT

Polyurethane article black colorants which comprise a novel blue polymeric anthraquinone colorant, rather than the previous standard polymeric triphenylmethane blue-type colorants are provided. Such a novel blend of colorants to produce black colorations within the target polyurethane foams exhibits very low color degradation within polyurthane foams, primarily due to the stability and resiliency of the novel anthraquinone-based polymeric colorant in the presence of high isocyanate levels, as well as large amounts of reactive tertiary amines (from catalyst residue, for example). A black colorant comprising such a novel blue polymeric colorant, as well as polyurethane foams comprising such a novel black coloring agent and methods of producing such foams are all contemplated within this invention.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 10/036,285,filed on Oct. 26, 2001, now U.S. Pat. No. 6,642,283. This parentapplication is herein entirely incorporated by reference.

FIELD OF THE INVENTION

This invention relates to polyurethane article black colorants whichcomprise a novel blue polymeric anthraquinone colorant, rather than theprevious standard polymeric triphenylmethane blue-type colorants. Such anovel blend of colorants to produce black colorations within the targetpolyurethane foams exhibits very low color degradation duringpolyurethane foam formation, primarily due to the stability andresiliency of the novel anthraquinone-based polymeric colorant in thepresence of high isocyanate levels, as well as large amounts of reactivetertiary amines (from catalyst residue, for example). A black colorantcomprising such a novel blue polymeric colorant, as well as polyurethanefoams comprising such a novel black coloring agent and methods ofproducing such foams are all contemplated within this invention.

BACKGROUND OF THE PRIOR ART

This invention relates to a novel black colorant composition, whichexhibits very low color degradation during the execution of polyurethanefoams. The colorant composition may be incorporated into a resin.

A material will appear black if substantially all of the light in thevisible electromagnetic spectrum (400-700 nanometer) is absorbed. Thus,black colorant compositions may be mixtures of two, three or moreindividual colorants, which compliment each other to absorb light acrossthe spectrum. For example, orange and blue; yellow, red and blue; andorange, blue and purple represent color combinations which will create ablack composition.

In general, a black colorant composition made by combining two or morecolorants will absorb electromagnetic radiation across the entirevisible spectrum, but the absorbance at each wavelength may not beuniform. Consequently, the absorbance of such a composition may berepresented by a series of peaks and valleys across the visiblespectrum. Loss or modification of any of the component results in changeof hue of the black. Such color loss may be caused by any number ofconditions however, it has been realized that certain blue polymericcolorants, such as certain triphenylmethane and/or anthraquinone types,that actual degradation of the compounds themselves contributes mostprominently to such deleterious color shifts, particularly within foamarticles.

Polymeric colorants have become the preferred coloration method inindustry for polyurethane products, such as foams, resins, and the like.Being liquid in nature, these polymeric colorants contain hydroxylterminated polyoxyalkylene chain (or chains) and actually tend to reactto and within the urethane during polymerization. As a result, the coloris integrated within the foam and provides excellent uniformity anddepth throughout the entire article. Generally, these colorations areperformed in situ during foam, resin, etc., formation. For instance,polymeric colorants (i.e., polyoxyalkylenated colorants), such as thosedescribed in U.S. Pat. No. 4,284,279 to Cross et al., have beenintroduced within polyol compositions during slabstock foam production.The “colored” polyol then reacts with an isocyanate composition to formthe desired colored foam. Such foamed products require the presence of acatalyst or catalysts to effectuate the desired reaction between thepolyol and isocyanate components. The most prevalent catalysts, due tocost in using, and disposing, are tertiary amine-based compounds, Toreduce emissions of residual amine catalysts, the industry has turned tousing hydroxyl-terminated type amine catalysts, most notably DMEA andDABCO TL catalysts (a blend of triethylene diamine and2-{[2-dimethylamino)ethyl]methylamino}ethanol) and Texacot ZF10(N,N,N′-trimethl-N′-hydroxyethyl-bis(aminoethyl)ether). These catalystsunfortunately present the ability to exaggerate certain problems withinthe resultant foams, most notably color loss and/or degradations.Apparently, such catalysts could react with colorants such as TPM-basedchromophores as disclosed in U.S. Pat. Nos. 4,992,204 to Kluger et al.,during polyurethane formation. The high temperatures associated withpolyurethane foam production permits attack of the positively chargedTPM polymeric colorants, such as Reactint® Blue X3LV (from MillikenChemical). With a strong positive charge on the base carbon of such aTPM chromophore, the hydroxyls present within the catalyst are drawn tothe colorant and appear to react in some fashion to weaken the necessarystrong color-producing positive charge. Such deleterious weakening ofthe TPM color strength (through the believed degradation of the actualcolorant structure itself), thus apparently causes a severe reduction incolor and/or a shift of hue within the foam media. Seemingly, such hightemperature discolorations and degradations more readily occur betweenabout 15 and 60 minutes after foam generation (after gelation andblowing of the foam-producing composition) has taken place. Without thepresence of environmentally unfriendly and thus avoided CFC auxiliaryblowing agents, such an exothermic reaction reaches higher temperaturesthat exaggerate the problem and thus need alternate methods ofdissipation in order to permit color retention of the previouslyutilized blue colorant components of the standard black colorantformulation. Due to the insulating effect of polyurehtane foams as well,these high temperatures are also retained for several hours, if notdays, also permitting exaggeration of this problem. Thus, in effect thehigh temperatures generated in such a manner increase the rate of attackby the hydroxyl of the catalyst on the TPM constituents. As a result,discrete areas within the middle of the final article are most likediscolored as compared with the remaining portions of the article.

One specific issue exists in the utilization of polymerictriphenylmethane colorants as components within black formulations, suchas within Reactint® Black X77 (from Milliken Chemical), for thecoloration of polyurethane foam articles (as mentioned above). Such TPMcolorants, which comprise highly desirable polyoxyethylene chains,polyoxypropylene chains, or both, provide extremely effectivecolorations to target polyurethane media. However, as noted above,certain polymerization catalysts, which happen to be some of the desiredcatalysts throughout the industry, tend to attack the TPM chromophore atthe positively charged carbon center and/or the nitrogen linking groups(present between the TPM backbone and the polymeric chains), therebydegrading the colorants themselves and/or changing the hue thuspreventing effective colorations of the target foam article. The targetblack colorant formulations thus suffer greatly in terms of colorretention and exhibit color loss or shade modification (e.g., loss ofblue colorant components while leaving the remaining primary colorantsconstituting the uneffected blend which, as these are generally mixturesof red, yellow, violet, orange, etc., colorants, result in actual shadeshifts away from the desired black) as a result of this problem. Tosolve the above-noted degradation issue, certain anthraquinone-basedpolymeric colorants, including those disclosed in U.S. Pat. No.4,137,243 to Farmer, and U.S. Pat. No. 4,846,846 to Rekers et al., havebeen utilized as an alternative to such TPM-based types for polyurethanefoam end-uses. Certain anthraquinone-based blue polymeric colorants havealso been utilized as components to replace TPM blues within blackformulations, such as within Reactint® Black 2256 (from MillikenChemical). Although such anthraquinone-type polymeric colorants (such asReactint® Blue X17, from Milliken Chemical) are less susceptible todegradation due to amine catalyst residues, these previously usedpolymeric anthraquinones suffer similar degradation characteristics as aresult of the presence of higher levels of diisocyanate (hereinafter,“High TDI Index”, basically an amount in excess of about 15 weightpercent of isocyanate within the entire polyurethane formulation) withinthe target polyurethane foam pre-cursor formulation (such foams areproduced, generally, through the reaction of an isocyanate and a polyol)or the like.

As noted above, during polyurethane foam production, certain tertiaryamine-based hydroxyl-group containing catalysts (reactive aminecatalysts) have a tendency to attack the cationic carbon center and/ornitrogen linking groups within triphenylmethane (TPM) polymeric bluecolorants, such as those disclosed in U.S. Pat. No. 4,992,204 to Klugeret al., thus cause the loss of blue color, particularly at elevatedtemperatures associated with foam production, thereby reducing theircolor strength and/or shifting the hue of color within such finishedfoam articles. Although such tertiary amines do not appear to attack thealiphatic amino anthraquinone-based blue polymeric colorants, such asthose disclosed in U.S. Pat. No. 4,137,243 to Farmer, and U.S. Pat. No.4,846,846 to Rekers et al., to an extent to cause any appreciable colorloss, some of such blue colorants have a tendency to lose color strengthin (and thus exhibit a loss in stability within) polyurethane foamsystems utilizing an elevated isocyanate index (e.g., an excess ofisocyanate constituent in an amount above about 15% by total weight)and/or to the high exotherm generated during target foam formation, thuslimiting their widespread use within polyurethanes in general.Therefore, improved colorants, particularly blue colorants as componentswithin black colorant formulations for polyurethane foam products, arehighly desired to the extent that they exhibit versatility in eithertertiary amine catalyzed foams or high isocyanate index foams, as wellas other foam types. To date, the best blue polymeric colorants for sucha purpose are those noted above which, although they exhibit excellentstability within certain polyurethane media, and other like properties,they also exhibit a certain lack of versatility such that their use islimited to specific targeted foam types.

As a result, any marked improvements in such a manner are of utmostimportance within the polyurethane foam production industry. To date,again, there have been no significant or helpful improvements noradvancements disclosed within the pertinent prior art.

OBJECTS OF THE INVENTION

It is therefore an object of this invention to provide a novel stableblack colorant composition for the coloration of polyurethane article.It is a further object of this invention to provide a novel polymericblack colorant composition that exhibits high stability in the presenceof certain amine catalysts and/or high amounts of isocyanate (high TDIindex foams) during polyurethane article formation. Further objectivesof this invention are to provide a novel stable polymeric black colorantcomposition which may be used to color polyurethane foam; a blackcolorant composition comprised of at least a novel blue polymericaromatic amino anthraquinone colorant; and/or a black colorantcomposition comprised of at least one aromatic amine anthraquinonepoly(oxyalkylene)-substituted colorant. A further objective is toprovide a black coloration method for polyurethane production thateffectively reduces and/or eliminates color degradation and shift of huein association with the presence of either amine-based catalysts or highamounts of isocyanates therein.

SUMMARY OF THE INVENTION

Accordingly, this invention is directed to a black-colored polyurethanearticle comprising, as at least one colorant component, a blueanthraquinone colorant comprising at least one aromatic amine pendantgroup attached to the 1-, 4-, or both positions and which optionally,and preferably, exhibits at least one poly(oxyalkylene) chain attachedthrough said at least one aromatic amino group. Also encompassed withinthis invention is a black colorant formulation comprising the same bluecolorant as at least one colorant component therein. In particular, sucha blue colorant preferably is defined in accordance with the followingstructure of Formula (I)

wherein A is selected from the group consisting of hydrogen, C₁-C₈alkyl, C₁-C₈ alkoxy, and the structure of Formula (II)

and B is selected from the group consisting of hydrogen, C₁-C₈ alky,C₁-C₈ alkoxy, and the structure of Formula (III)

and wherein at least one of A and B is the structure of Formulas (II) or(III); wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are the sameor different and are selected from the group consisting of hydrogen,C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, and Q-E, wherein Q is selected from thegroup consisting of N, O, S, SO₂, SO₃, CO₂, SO₂N, alkyl, and alkoxy, andE conforms to the structure of Formula (IV)

[polyoxyalkylene constituent]_(z)R′  (IV)

wherein z is 1 or 2; polyoxyalkylene constituent is selected from thegroup consisting of at least three monomers of at least one C₂₋₂₀alkyleneoxy group, glydicol, glycidyl, or mixtures thereof, monomers ofat least one C₂₋₂₀ alkyleneoxy group, glydicol, glycidyl, or mixturesthereof; and R′ is selected from the group consisting of hydrogen, C₁₋₂₀alkyl, C₁₋₂₀ alkylester, halo, hydroxyl, thio, cyano, sulfonyl, sulfo,sulfato, aryl, nitro, carboxyl, C₁₋₂₀ alkoxy, amino, C₁₋₂₀ alkylamino,acrylamino, C₁₋₂₀ alkylthio, C₁₋₂₀ alkylsufonyl, C₁₋₂₀ alkylphenyl,phosphonyl, C₁₋₂₀ alkylphosphonyl, C₁₋₂₀ alkoxycarbonyl, and phenylthio;wherein at least one of R₁, R₂, R₃, R₄, or R₅ is Q-E and/or at least oneof R₆, R₇, R₈, R₉, or R₁₀ is Q-E. More preferable is the situationwherein said blue colorant conforms to the structure of (V)

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are the same ordifferent and are selected from the group consisting of C₁₋₂₀ alkyl,halo, hydroxyl, hydrogen, cyano, sulfonyl, sulfo, sulfato, aryl, nitro,carboxyl, C₁₋₂₀ alkoxy, and Q-E, wherein at least one of R₁, R₂, R₃, R₄,and R₅ is Q-E, and/or at least one of R₆, R₇, R₈, R₉, or R₁₀ is Q-E,wherein Q is selected from the group consisting of N, O, S, SO₂, SO₃,CO₂, and E is represented by the Formula (VI)

[polyoxyalkylene constituent]_(z)R′  (VI)

wherein z is 1 or 2; polyoxyalkylene constituent is selected from thegroup consisting of at least three monomers of at least one C₂₋₂₀alkyleneoxy group, glydicol, glycidyl, or mixtures thereof, monomers ofat least one C₂₋₂₀ alkyleneoxy group, glydicol, glycidyl, or mixturesthereof, and R′ is selected from the group consisting of hydrogen, C₁₋₂₀alkoxy, C₁₋₂₀ alkyl, and C₁₋₂₀ esters. Preferably, when structure (V) ispresent, the following conditions are met: R₃ is Q-E and R₁, R₂, R₄, andR₅ are all hydrogen; R₈ is Q-E and R₆, R₇, R₉, and R₁₀ and are allhydrogen; wherein Q is O; polyoxyalkylene constituent is selected fromthe group consisting of from 3 to 50 moles of ethylene oxide and acombination of from 2 to 20 moles of ethylene oxide and from 1 to 20moles of propylene oxide; z is 1; and R′ is hydrogen. More specificcompounds of this type of shown below as well.

Also encompassed within this invention is a method of producing a blackpolyurethane article comprising the steps of: a) providing a polyolcomposition; b) providing an isocyanate composition; wherein at leastone of the compositions of steps “a” and “b” comprises a black colorantformulation comprising at least one blue polymeric anthraquinonecolorant as defined above; and c) reacting all of the compositions fromsteps “a”, and “b”, together in the presence of either a tertiary aminehydroxy-containing catalyst or in the presence of any other typecatalyst but with an amount of isocyanate in excess of 15% by weight ofthe total reaction mixture. A polyurethane article, preferably thoughnot necessarily a foam article, produced by these methods and/orexhibiting a substantially uniform black coloration throughout is alsocontemplated within this invention, particularly in the presence ofeither of said tertiary amine hydroxy-containing catalyst and/or in thepresence of such a large amount of isocyanate (including mono, di,and/or polyisocyanates) reactant.

In general, polyurethane foam is produced through the catalyzedpolymerization of the reaction products of polyols and isocyanates. Sucha reaction is well known throughout the polyurethane industry and hasbeen practiced for many years. The potential number and types of polyolsutilized within this invention are plentiful. Such a compound is definedas comprising at least two alcohol moieties, preferably at least three.The free hydroxyl groups react well with the isocyanates to form theurethane components which are then polymerized to form the desiredpolyurethanes. Blowing agents present within the polymerization stepprovide the necessary foam-making capability. Preferred polyols thuscomprise between three and six alcohol moieties, comprising from betweenone and six carbon atoms per alcohol moiety. Most preferred is a typicaltrifunctional polyol, such as F3022 polyol, available from Lyondell.

Isocyanates, most preferred diisocyanates, are well known components ofsuch polyurethane foams and include any compounds which possess at leastone free cyanate reactive group, and most preferably two, although moremay be utilized. Such compounds may also be aliphatic or aromatic innature. The most prominently utilized isocyanates, and thus the mostpreferred types for this invention, are toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), and methylene diisocyanate. Thepolyol is generally reacted with a slight excess of isocyanate (ratio offrom 1:0.85 to 1:1.25) to produce a soft flexible foam product; thegreater the ratio, the harder the produced foam). For rigid foams theexcess isocyanate index is substantially higher (1:2.0 to 1:4.0). Inpractice, two separate streams of liquids (one of polyol, the other ofisocyanate) are mixed together in the presence of a polymerizationcatalyst and a blowing agent in order to produce the desiredpolyurethane foam product. As noted above, regular polymericanthraquinone blue colorants, including aliphatic amino anthraquinonesappear to react with such excess amounts of isocyanate and exhibit lossof color and/or change of hue in the final target polyurethane articles.

As noted above, this invention is directed to polyurethanes in general,with foam articles most preferred. Thus, laminates, solid articles, andany other type of colored polyurethane, is encompassed within thisinvention.

The term “tertiary amine-based hydroxy-containing catalyst” is intendedto encompass any reactive amine catalysts including the gelation/blowingcatalysts utilized within polyurethane production which comprises atleast one amine constituent. As noted above, amine-based catalysts, andmore specifically, tertiary amine catalysts, are widely utilized withinsuch specific foam-producing methods. Two catalysts, in particular,DABCO TL and DMEA, are excellent gelation/blowing catalysts for thispurpose; however, they also appear to be extremely reactive with andcould readily attack unmatched species such as cationic carbon centerand/or nitrogen-containing moieties on the phenyl rings of TPMcolorants. As noted above, oxidation by the amine readily occurs uponexposure to high temperatures, thus resulting in the undesirablescorched foam portions. Although any amine presents such a potentialreactivity (oxidation) problem, and thus is contemplated within thescope of this invention, it has been found that the highly reactivetertiary amines present greater threats to discoloration and degradationto the final foam product. The amount of tertiary aminehydroxy-containing catalyst required to effectuate the desired urethanepolymerization is extremely low, from between 0.05 php to about 1.00 phpof the entire foam-making composition; more specifically, such a rangeis from about 0.07 php to about 0.60 php. Even though the number of freeamines available are quite low, their ability to deleteriously affectthe final foam product through oxidation of free reactive groups(hydroxyls, for example) within colorants, polyols, and other additives,is pronounced upon exposure to high temperature during polymerization.

Such discolorations and/or color degradations are much reduced or do notoccur when the TPM component is replaced with the specific inventivearomatic amine-based anthraquinone polymeric blue colorant as definedabove. Other coloring agents may be also added within the differentstreams prior to reaction and/or polymerization as well. Such additionsare well known within the industry to produce colored polyurethane foamarticles in various colors and shades. Thus, the term “coloring agent”is intended to encompass any pigment, pigment dispersion, polymericcolorant (other than the required at least one anthraquinone type), dye,dyestuff, any mixtures thereof, and the like, which provides desirablecolorations to target polyurethane foam articles. In general, suchcoloring agents are added to the polyol stream (prior to reaction withthe isocyanate) in amounts ranging from about 0.001 php to about 10 php.Higher color loadings may provide certain migratory, crocking, and/orbleeding problems. Suitable pigments for this invention include, withoutlimitation, carbon black, lamp black, titanium dioxide, phthalocyanine,and the like. Suitable polymeric colorants for this purpose aredisclosed within Cross et al., again without any limitation, and asmerely examples: Suitable dyes and dyestuffs include reactive dyes,solvent dyes, vat dyes, and the like.

Other additives or solvents may also be present within the foam-makingcomposition. Auxiliary blowing agents are required to provide thenecessary foam blowing capability and reduce chances of combustion. Suchcompounds include methylene chloride, acetone, carbon dioxide (which maybe liberated during the reaction between water and isocyanate), and thelike, and are present in amounts of between about 1.0 php and 10 php ofthe entire foam-making composition. Water may thus also be added inrelatively low amount (i.e., from about 1.5 to about 10 pbp; mostpreferably between about 3 and 5.5 php) to provide carbon dioxide forblowing purposes. Silicones may be added to provide desired cellstructure and foam stability and are present in an amount from about 0.1to about 2 php of the entire foam-making composition; preferably fromabout 0.5 to about 1.6 php.

The desired black colorant is thus produced through the utilization ofsuch a novel inventive blue anthraquinone-based aromatic amino polymericcolorant, as well as any other components, including, for example, red,yellow, and, possibly, violet and/or orange, as noted in greater detail,below.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Initially, the desired novel inventive blue anthraquinone colorants wereproduced in accordance with the following procedures:

Synthesis of Intermediates EXAMPLE 1

Ethanol (200 proof, 515 g) and p-aminophenol (300 g, 2.75 mol) werecharged into a 2L 3-neck round bottom flask equipped with a thermometerand a condenser. Benzaldehyde (292 g, 2.75 mol) was added from anadditional funnel while maintaining a slow and steady flow and whilestirring. Another portion of ethanol (150 g) was added and the wholemixture was heated to reflux for 1.5 h. After cooling down to roomtemperature, the solid thus formed was collected by filtration andwashed three times with ethanol (3×50 ml) and dried. 492 g (91%) ofimine product was obtained as a pale yellow powder.

The imine product (285 g, 1.44 mol, from Example 1) was reacted with 634g of ethylene oxide in 200 ml of toluene, according to the proceduresdescribed in U.S. Pat. Nos. 5,082,938 and 5,591,833, to yield 910 g(98.2%) of pale brown yellow liquid product.

EXAMPLE 3

The imine product (1182 g, 6 mol, from Example 1) was reacted, accordingto the procedures described in U.S. Pat. Nos. 5,082,938 and 5,591,833,with ethylene oxide (528 g, 12 mol), propylene oxide (696 g, 12 mol),and ethylene oxide (1056 g, 24 mol), respectively, in 1400 ml of tolueneto yield 3360 g (97%) of the product depicted above as a pale brownyellow liquid.

EXAMPLE 4

4-Nitrophenol (556 g, 4 mol) was allowed to reacted in toluene (750 g),according to the procedures described in U.S. Pat. No. 5,135,972, withethylene oxide (352 g, 8 mol), propylene oxide (464 g, 8 mol) andethylene oxide (704 g, 16 mol), respectively, to generate 2034 g (98%)of the nitrophenol product depicted above as a pale yellow liquid.

EXAMPLE 5

The imine product of Example 2 (340 g, 0.27 mol) was hydrolyzed in thepresence of water (150 ml) and hydrochloric acid (56 g) to generate 285g (97%) of the alkoxylated aniline product depicted above as a lightbrownish yellow liquid.

EXAMPLE 6

Alternative methods of forming such an intermediate have been followed,such as the following:

Method 1: The imine product of Example 3 (600 g) was hydrolyzed in thepresence of water (220 g) and concentrated hydrochloric acid (45 g) orsulfuric acid (15 g) to result in 493 g of the aniline product depictedabove as a light brownish yellow liquid.

Method 2: The nitrophenol product of Example 4 (913 g) was hydrogenatedin the presence of Pd/C (5%, 10 g) in methanol, according to theprocedures described in U.S. Pat. Nos. 5,135,972 and 5,082,938, to yield804 g of the aniline product depicted above as a pale yellow liquid.

Synthesis of Inventive Polymeric Arylamino Anthraquinone Blue ColorantsEXAMPLE 7

To a 500-ml 3-neck round-bottom flask equipped with a mechanicalstirrer, a thermal controller and a reflux condenser, were charged 26.4g of quinizarin, 9 g of leucoquinizarin, 12 g of boric acid and 60 g ofwater. After stirred for 10 min under nitrogen gas, the mixture was thencharged with 170 g of the alkoxylated aniline product of Example 5. Thewhole formulation was then heated to 120° C. with a nitrogen gas sweepand the reaction was monitored by UV-vis. After 8 hours of heating, thereaction was complete (UV-vis in MeOH, Abs. λ_(632 nm)/λ_(600 nm)>1.03).The reaction mixture was neutralized to pH 6-7 by caustic. Upon removalof water by vacuum stripping, 200 g of the desired product (depicted bythe formula above) was obtained as a viscous blue liquid with acolor-strength of 8.8 abs./g/L (MEOH) and the maximum absorbency at 632nm.

EXAMPLE 8

Alternative methods of producing such a colorant exist as follows:

Method 1: To a 250-ml 3-neck round-bottom flask equipped with amechanical stirrer, a thermal controller and a reflux condenser, werecharged 10.6 g (44 mmol) of quinizarin, 3.6 g (15.2 mmol) ofleucoquinizarin, 24 g of water and 4.8 g (78 mmol, 1.3 eq) of boricacid. After stirring for 10 min under nitrogen gas, the mixture was thencharged 64 g (2.2 eq) of the ethoxylated aniline product of Example 6.The whole formulation was heated to 120° C. with a nitrogen gas sweepand the reaction was monitored by UV-vis. After 9 hours of heating, thereaction was complete (UV-vis in MeOH, Abs. λ_(432 nm)/λ_(600 nm)>1.03).After the addition of 80 ml water and neutralization to pH 7-8, themixture was poured into a separation funnel to settle, and the organiclayer was collected. Upon removal of water by vacuum stripping, 46 g ofthe desired product (depicted by the formula above) was obtained as aviscous blue liquid with a color-strength of 12.5 abs./g/L (MeOH) andthe maximum absorbency at 631 nm.

Method 2: To a 500-ml 3-neck round-bottom flask equipped with amechanical stirrer, a thermal controller and a reflux condenser, werecharged 26.4 g (110 mmol) of quinizarin, 9 g (38 mmol) ofleucoquinizarin, 60 g of water and 12 g (200 mmol, 1.3 eq) of boricacid. After stirred for 10 min under nitrogen, the mixture was thencharged 172 g of the ethoxylated aniline product of Example 6. The wholeformulation was heated to 120° C. with a nitrogen gas sweep and thereaction was monitored by UV-vis. After 5 hours of heating, the reactionwas complete (UV-vis in MeOH, Abs. λ_(632 nm)/λ_(600 nm)>1.03). Afterthe addition of 100 ml water and neutralized to pH 7-8, the mixture waspoured into a separation funnel to settle, and the organic layer wascollected. The organic layer was then washed 3 times with 130 ml of 20%aqueous ammonia solution. Upon removal of water from the organic layerby vacuum stripping, 172 g of the desired product was obtained as aviscous blue liquid with a color-strength of 10.8 abs./g/L (MeOH) andthe maximum absorbency at 631 nm.

Method 3: To a 2000-ml 3-neck round-bottom flask equipped with amechanical stirrer, a thermal controller and a reflux condenser, werecharged 105.6 g of quinizarin, 36 g of leucoquinizarin, 240 g of waterand 48 g of boric acid. After stirred for 10 min under nitrogen gas, themixture was then charged with 752 g of the ethoxylated aniline productof Example 6. The whole formulation was then heated to 120° C. with anitrogen gas sweep and the reaction was monitored by UV-vis. After 16hours of heating, the reaction was complete (UV-vis in MeOH, Abs.λ_(632 nm)/λ_(600 nm)>1.03). The mixture was cooled to room temperatureand washed 3 times with 600 ml of 3% H₂SO₄ solution and 1 time with 600ml of 20% aqueous ammonia solution. Upon removal of water from theorganic layer by vacuum stripping, 600 g of the desired product wasobtained as a viscous blue liquid with a color-strength of 11.3 abs./g/L(MeOH) and the maximum absorbency at 630 nm.

Method 4: To a 250-ml 3-neck round-bottom flask equipped with amechanical stirrer, a thermal controller and a reflux condenser, werecharged 9 g (37.4 mmol) of quinizarin, 9 g (38 mmol) of leucoquinizarinand 20 g of water. After stirring for 10 min under a nitrogen gas purge,the mixture was then charged 160 g of the ethoxylated aniline product ofExample 6 and 12 g (0.2 mol) of boric acid. The whole formulation wasthen heated to 120° C. with a nitrogen gas sweep. In the meantime, 17.5g (72.4 mmol) of quinizarin was mixed together to make slurry. After 3hours of heating at 120° C., portions of 14 g of quinizarin/water slurrywas charged into above reaction mixture every hour until it finished.After the last addition, the reaction mixture was continued heating for3 more hours until the reaction was complete (UV-vis in MeOH, Abs.λ_(632 nm)/λ_(600 nm)>1.03). The mixture was cooled to room temperatureand washed 3 times with 130 ml of 20% aqueous ammonia solution and theorganic layer was collected. Upon removal of water from the organiclayer by vacuum stripping, 160 g of the desired product was obtained asa viscous blue liquid with a color-strength of 10.1 abs./g/L (MEOH) andthe maximum absorbency at 632 nm.

Polyurethane Foam Article Production

Polyurethane foam articles were produced to investigate anydiscolorations and/or degradations. Such foams were produced through thereaction of the following components:

REACTIVE AMINE CATALYST POLYURETHANE FOAM COMPOSITION Component Amountin mL F3022 Polyol (Lyondell) 100 Water 4.53 DABCO TL (catalyst from AirProducts) 0.15 DABCO T10 (catalyst) 0.30 L520 Silicone (from Witco) 1.080/20 toluene diisocyanate 49.0 Black Colorant (as listed below) 0.9

Two comparative, standard black colorants (Comparative Black ColorantComposition 1 and 2) were tested and comprised either REACTINT® BlueX3LV, a triphenylmethane polymeric colorant comprising polyoxyethyleneand polyoxypropylene chains, or REACTINT® BLUE X17, an aliphatic aminoanthraquinone-based polymeric colorant, not aromatic amino-based. Thecompositions were as follows:

COMPARATIVE BLACK POLYMERIC COLORANT COMPOSITION #1 Component Amount (inweight percent) REACTINT ® Blue X3LV 36.6 (from Milliken & Company)REACTINT ® Yellow X15 29.0 REACTINT ® Red X64 27.2 REACTINT ® Violet X807.2

COMPARATIVE BLACK POLYMERIC COLORANT COMPOSITION #2 Component Amount (inweight percent) REACTINT ® Blue X17 50.3 REACTINT ® Orange X96 43.2REACTINT ® Red X64 6.5

One preferred embodiment of the inventive black colorant formulation isthe following and was tested in comparison with these two Compositions:

INVENTIVE BLACK POLYMERIC COLORANT COMPOSITION Component Amount (inweight percent) Blue from EXAMPLE 8 73.4 REACTINT ® Yellow X15 12.8REACTINT ® Red X64 13.8

Reactive Amine Catalyst Stability Testing

The Inventive black composition and comparative black colorantcomposition 1 were introduced within individual foam production methodsto form target polyurethane foam articles of the same foam formulationas noted above. Upon mixture within a reaction vessel, the reaction ofthe polyol and isocyanate (and other components, including thecolorants) created a “health” bubble (indicating gelation and blowingbalance), and the vessel was then exposed to 200° C. (generated within amicrowave oven to simulate actual temperatures encountered on anindustrial production level) for about 10 minutes. The resultant foambun was then sliced in half and analyzed empirically. A clear area ofdiscoloration within the center of the bun and extending about 4 inchesin each direction was immediately noticed for the comparativepolyurethane article made with comparative black composition 1. Also,the same area exhibited a brittle foam possessing characteristicstotally different from that of the properly colored foam portions. Suchfoam articles would be considered off-quality and thus would requiredisposal. The inventive foam article made from the inventive blackcomposition was also analyzed; no noticeable discoloration orbrittleness was observed and thus were acceptable for use.

High TDI Index Stability Test

First, the same procedures but with a different amine catalyst (DABCO33LV, a triethylene diamine-type in an amount of 0.15 mL, instead of0.15 ml of DABCO TL) were followed to make standard foam articles (fromthe inventive black composition only to show compatability withdifferent catalysts with lower amounts of isocyanate). The sameprocedures were again followed, however, this time 55 mL of theisocyanate (at an Index of 1.25 for the TDI; an amount in excess ofabout 15 weight % for the total composition) and the different aminecatalyst (DABCO 33LV, a triethylene diamine-type in an amount of 0.15mL, instead of 0.15 ml of DABCO TL), were utilized to prepare samplefoam articles from both the inventive black composition and thecomparative black composition #2. All of these samples (three differentones) were then analyzed after slicing through the middle of eachrespective foam bun and evaluating the change in color between theexterior of the foam and the very interior of the same foam article (bycomparing the reading in CMC for delta E with an UlstraScans XESpectrophotometer from HUnterLab). The results are tabulated below witha lower value being more desirable (and thus indicating greater coloruniformity throughout the entire article). The sample numbers below arenoted for the colorant composition used, with samples 2 and 3 being theHigh TDI Index foam formulations.

EXPERIMENTAL TABLE E Values for Sample Foams Sample Number ColorantComposition Used delta E Value 1 Inventive Black 4.73 2 Inventive Black4.69 3 Comparative Black #2 10.3

Thus, while exposure to different catalysts and a high TDI index, theinventive samples (1 and 2) exhibit far improved color retention andthus performance when compared to the standard formulation comprising acommercial blue polymeric colorant component (REACTINT® Blue X17) forthe black colorant formulation therein.

Thus, in summation, with reactive amine catalyst residues, the novelblack formulations were far more effective at color retention (and thuscolor uniformity) than the comparative black formulations. Likewise, thehigh isocyanate amount foam articles exhibited far better results incolor retention for the inventive black formulations than for thestandard, prior formulations.

While the invention will be described and disclosed in connection withcertain preferred embodiments and practices, it is in no way intended tolimit the invention to those specific embodiments, rather it is intendedto cover equivalent structures structural equivalents and allalternative embodiments and modifications as may be defined by the scopeof the appended claims and equivalence thereto.

What we claim is:
 1. A method of producing a black polyurethane foamarticle comprising the steps of: a) providing a polyol composition; b)providing an isocyanate composition; wherein at least one of thecompositions of steps “a” and “b” comprises a black colorant formulationcomprising, as at least one colorant component, a blue anthraquinonecolorant having at least one poly(oxyalkylene) chain is attached throughat least one aromatic amino group, to the 1-, 4, or both positions ofsaid anthraquinone colorant; and wherein said blue anthraquinonecolorant conforms to the structure of Formula (I)

wherein A is selected from the group consisting of hydrogen, C₁-C₈alkyl, C₁-C₈ alkoxy, and the structure of Formula (II)

and B is selected from the group consisting of hydrogen, C₁₋₈ alkyl,C₁-C₈ alkoxy, and the structure of Formula (III)

and wherein at least one of A and B is the structure of Formulas (II) or(III); wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are the sameor different and are selected from the group consisting of hydrogen,C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy, and Q-E, wherein Q is selected from thegroup consisting of N, O, S, SO₂, SO₃, CO₂, SO₂N, alkyl, and alkoxy, andE conforms to the structure of Formula (IV) [polyoxyalkyleneconstituent]_(z)R′  (IV) wherein z is 1 or 2; polyoxyalkyleneconstituent is selected from the group consisting of at least threemonomers of at least one C₂₋₂₀ alkyleneoxy group, glydicol, glycidyl, ormixtures thereof, monomers of at least one C₂₋₂₀ alkyleneoxy group,glydicol, glycidyl, or mixtures thereof; and R′ is selected from thegroup consisting of hydrogen, C₁₋₂₀ alkyl, C₁₋₂₀ alkylester, halo,hydroxyl, thio, cyano, sulfonyl, sulfo, sulfato, aryl, nitro, carboxyl,C₁₋₂₀ alkoxy, amino, C₁₋₂₀ alkylamino, acrylamino, C₁₋₂₀ alkylthio,C₁₋₂₀ alkylsufonyl, C₁₋₂₀ alkylphenyl, phosphonyl, C₁₋₂₀alkylphosphonyl, C₁₋₂₀ alkoxycarbonyl, and phenylthio; wherein at leastone of R₁, R₂, R₃, R₄, or R₅ is Q-E and/or at least one of R₆, R₇, R₈,R₉, or R₁₀ is Q-E; and c) reacting all of the compositions from steps“a”, and “b” together in the presence of either a tertiary aminehydroxy-containing catalyst or in the presence of any other typecatalyst but with an amount of isocyanate in excess of 15% by weight ofthe total reaction.
 2. A method of producing a black polyurethane foamarticle comprising the steps of: a) providing a polyol composition; b)providing an isocyanate composition; wherein at least one of thecompositions of steps “a” and “b” comprises the black colorantformulation as defined in claim 1, wherein said blue anthraquinonecolorant conforms to the structure of Formula (V)

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ are the same ordifferent and are selected from the group consisting of C₁₋₂₀ alkyl,halo, hydroxyl, hydrogen, cyano, sulfonyl, sulfo, sulfato, aryl, nitro,carboxyl, C₁₋₂₀ alkoxy, and Q-E, wherein at least one of R₁, R₂, R₃, R₄,and R₅ is Q-E, and/or at least one of R₆, R₇, R₈, R₉, or R₁₀ is Q-E,wherein Q is selected from the group consisting of N, O, S, SO₂, SO₃,CO₂, and E is represented by the Formula (VI) [polyoxyalkyleneconstituent]₂R′  (VI) wherein z is 1 or 2; polyoxyalkylene constituentis selected from the group consisting of at least three monomers of atleast one C₂₋₂₀ alkyleneoxy group, glydicol, glycidyl, or mixturesthereof, monomers of at least one C₂₋₂₀ alkyleneoxy group, glydicol,glycidyl, or mixtures thereof, and R′ is selected from the groupconsisting of hydrogen, C₁₋₂₀ alkoxy, C₁₋₂₀ alkyl, and C₁₋₂₀ esters; andc) reacting all of the compositions from steps “a”, and “b” together inthe presence of either a tertiary amine hydroxy-containing catalyst orin the presence of any other type catalyst but with an amount ofisocyanate in excess of 15% by weight of the total reaction.
 3. A methodof producing a black polyurethane foam article comprising the steps of:a) providing a polyol composition; b) providing an isocyanatecomposition; wherein at least one of the compositions of steps “a” and“b” comprises the black colorant formulation as defined in claim 2,wherein R₃ is Q-E and R₁, R₂, R₄, and R₅ are all hydrogen; R₈ is Q-E andR₆, R₇, R₉, and R₁₀ and are all hydrogen; wherein Q is O;polyoxyalkylene constituent is selected from the group consisting offrom 3 to 50 moles of ethylene oxide and a combination of from 2 to 20moles of ethylene oxide and from 1 to 20 moles of propylene oxide; z is1; and R′ is hydrogen; and c) reacting all of the compositions fromsteps “a”, and “b” together in the presence of either a tertiary aminehydroxy-containing catalyst or in the presence of any other typecatalyst but with an amount of isocyanate in excess of 15% by weight ofthe total reaction.
 4. A black polyurethane foam article produced by themethod of claim
 1. 5. A black polyurethane foam article produced by themethod of claim
 2. 6. A black polyurethane foam article produced by themethod of claim 3.